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Method for producing nitrobenzene compound

a nitrobenzene compound and nitrobenzene technology, applied in the field of nitrobenzene compound production, can solve the problems of no synthesis method for producing a 2,6-disubstituted nitrobenzene compound, and the target 2,6-disubstituted nitrobenzene compound cannot be obtained with good yield, etc., to achieve clean and excellent oxidant, easy to obtain, and low cost

Inactive Publication Date: 2014-06-12
IHARA CHEM IND CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Benefits of technology

The present invention provides a novel industrial production method for a nitrobenzene compound that is useful for making various organic compounds. This method uses an aniline compound and hydrogen peroxide as raw materials, without the need for high concentration hydrogen peroxide, which can be dangerous and difficult to handle. The method is simple, safe, inexpensive, and efficient, with a high yield and can be implemented on an industrial scale. Additionally, the invention avoids the use of phosphoric acid, which can cause environmental pollution, and uses waste acids that do not cause problems with the environment when neutralized.

Problems solved by technology

However, when an attempt is made to conduct the oxidation of a 2,6-disubstituted aniline compound under the same conditions, the target 2,6-disubstituted nitrobenzene compound cannot be obtained with good yield (see Comparative Examples 1 and 2).
Therefore, conventionally, it has been necessary to use high concentration hydrogen peroxide, which requires much caution in work, and further use a high risk organic peroxy acid such as peracetic acid or trifluoroperacetic acid in order to obtain a 2,6-disubstituted nitrobenzene compound from a 2,6-disubstituted aniline compound (Non Patent Literature 1 and Non Patent Literature 2), and there has been no synthesis method for producing a 2,6-disubstituted nitrobenzene compound under mild conditions.

Method used

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  • Method for producing nitrobenzene compound

Examples

Experimental program
Comparison scheme
Effect test

example 1

Production of 2,6-Dichloronitrobenzene

[0161]1.32 g (4.0 mmol) of sodium tungstate dihydrate and 4.0 g (40 mmol) of concentrated sulfuric acid were added to a solution of 16.2 g (100 mmol) of 2,6-dichloroaniline in 120 ml of methanol, and the mixture was heated to 40° C. 30 ml (291 mmol) of a 30% hydrogen peroxide solution was added dropwise over 10 hours. The pH value at this time was 0.5. After the completion of the dropwise addition, the mixture was stirred at 40° C. for 9 hours. After the disappearance of the 2,6-dichloroaniline was confirmed by gas chromatography (area percentage method), a solution of 9.8 g (150 mmol) of 86% potassium hydroxide in 24.3 ml of methanol was added dropwise while the temperature of the reaction liquid was adjusted to 40° C. or less. After the completion of the dropwise addition, the mixture was stirred at room temperature for 2 hours, and the reaction was completed. After the completion of the reaction, 95 ml of toluene and 32 ml of water were added...

example 2

Production of Methyl 3-Chloro-2-nitrobenzoate

[0163]A solution of 5.3 g (16.2 mmol) of sodium tungstate dihydrate and 3.2 g (32.3 mmol) of concentrated sulfuric acid in 53 ml of methanol was heated to 40° C., and a solution of 15 g (80.8 mmol) of methyl 2-amino-3-chlorobenzoate in 13 ml of methanol, and 33.0 ml (323 mmol) of a 30% hydrogen peroxide solution were simultaneously added dropwise over 10 hours. The pH value at this time was 0.5. After the completion of the dropwise addition, the mixture was stirred at 40° C. for 2 hours. After the disappearance of the methyl 2-amino-3-chlorobenzoate was confirmed by HPLC analysis (area percentage method), 30 ml of toluene and 8.3 ml (80.8 mmol) of a 30% hydrogen peroxide solution were added to the reaction liquid, and 19.9 g (88.9 mmol) of a 25% aqueous potassium hydroxide solution was further added dropwise so that the temperature was 30° C. or less. The mixture was stirred at room temperature for 12 hours, and the reaction was completed...

example 3

Production of 2,6-Dichloronitrobenzene

[0165]0.66 g (2.64 mmol) of tungstic acid and 0.40 g (1.23 mmol) of tetrabutylammonium bromide were added to a suspension of 2.0 g (12.3 mmol) of 2,6-dichloroaniline in 6 ml of water, and the mixture was heated to 40° C. 4.9 g (43.1 mmol) of a 30% hydrogen peroxide solution was added. The pH value at this time was 1.5. Then, the mixture was stirred at 40° C. for 16 hours. After the disappearance of the 2,6-dichloroaniline was confirmed by gas chromatography (area percentage method), 3 ml of methanol and 3.49 g (30.8 mmol) of a 30% hydrogen peroxide solution were added, and 2.8 g (12.3 mmol) of a 25% aqueous potassium hydroxide solution was added dropwise while the temperature of the reaction liquid was adjusted to 40° C. or less. After the completion of the dropwise addition, the mixture was stirred at room temperature overnight, and the reaction was completed. After the completion of the reaction, 30 ml of toluene and 20 ml of water were added,...

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Abstract

A method for producing a nitrobenzene compound represented by general formula (2), wherein R1 and R5 are the same or different, and each is a halogen atom or another functional group, and R2, R3, and R4 are the same or different, and each is a hydrogen atom or another functional group, comprises oxidizing an aniline compound represented by general formula (1), wherein R1, R2, R3, R4, and R5 are the same as described above, with hydrogen peroxide in the presence of a tungsten compound under an acidic condition, followed by oxidation with hydrogen peroxide under a neutral to alkaline condition.

Description

TECHNICAL FIELD[0001]The present invention relates to a method for producing a nitrobenzene compound, particularly a 2,6-disubstituted nitrobenzene compound. This 2,6-disubstituted nitrobenzene compound is useful, for example, as intermediates for the synthesis of various organic compounds (for example, physiologically active organic compounds such as medicines and agrochemicals).BACKGROUND ART[0002]Nitrobenzene compounds, particularly 2,6-disubstituted nitrobenzene compounds, are widely known as intermediates for the synthesis of various organic compounds, as described above. Particularly, 2,6-dichloronitrobenzene is reported as an intermediate for synthesis for producing a compound described as an EP4 receptor antagonist (see Example 55, Patent Literature 1), or as an intermediate for synthesis for producing a compound described as a brakykinin B1 receptor antagonist (see Example 8 and Example 104, Patent Literature 2). In addition, it is also known as an intermediate for synthesi...

Claims

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Application Information

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Patent Type & Authority Applications(United States)
IPC IPC(8): C07C201/06
CPCC07C201/06
Inventor TANI, SHINKIYADOMATSU, NAMIIKUMI, AKIKOHIRANO, YUUKIIDO, TAKUYA
Owner IHARA CHEM IND CO LTD
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